Polymerization of organic epoxides using certain metallic oxides and metallo organo compounds



United States Patent POLYMERIZATION OF ORGANIC EPOXIDES US- ING CERTAIN METALLIC OXIDES AND METAL- LO ORGANO COMPOUNDS Marco A. Achon, Akron, Ohio, assignor to The General Tire & Rubber Company, Akron, Ohio, a corporation of Ohio No Drawing. Filed Jan. 18, 1961, Ser. No. 83,361

Claims. (Cl. 260--2) The present invention relates to the polymerization of organic epoxides. In particular, the present invention relates to methods for the preparation of materials useful as catalysts in the polymerization of said epoxides, to the materials themselves, and to methods for the polymerization of said epoxides employing novel catalytic material.

It is an object of the present invention to provide a method for the preparation of materials useful as catalysts or catalytic compositions in the polymerization of organic epoxides.

Another object of the present invention is to provide a composition useful as a catalyst or catalytic material in the polymerization of organic epoxides.

A further object is to provide a method for the polymerization of organic epoxides utilizing certain novel materials having catalytic properties to effect the desired polymerization.

These and other objects and advantages of the present invention will become more apparent to those skilled in the art from the following detailed description and examples.

According to the present invention it has been discovered that organic epoxide compounds can readily be polymerized by the use of at least one inorganic oxide of the group consisting of antimony trioxide, antimony tetraoxide, antimony penta oxide, boron oxide, chromium trioxide, stannous oxide and stannic oxide which have been activated with at least one organometallic compound selected from the group consisting of AlR CdR and ZnR where R is at least one hydrocarbon radical of from 1 to 20 carbon atoms and, preferably, is free of aliphatic unsaturation.

The oxides such as antimony trioxide, antimony tetraoxide, antimony pentaoxide, boron oxide, chromium trioxide, stannous oxide and stannic oxide should preferably be free or essentially free of occluded Water and water of crystallization. They, also, desirably should be in finely divided form or powdered. The oxides can be used singly or in mixtures. Of these oxides it is preferred to employ antimony trioxide which affords the best results on polymerization.

Examples of aluminum, cadmium and zinc organic compounds which can be employed in making the catalyst product of the present invention are trimethyl aluminum, triethyl aluminum, triphenyl aluminum, tributyl aluminum, triisobutyl aluminum, diethyl methyl aluminum, triethenyl aluminum, tri(Z-butenyl) aluminum, tricyclohexyl aluminum, tritolyl aluminum, tribenzyl aluminum, methyl-, ethyl-, cyclohexyl aluminum, tricyclobutenyl aluminum, diethyl phenyl aluminum, diphenyl cyclohexyl aluminum, trinaphthyl aluminum, tribiphenylyl aluminum, triheptyl aluminum, trieicosenyl aluminum, tripentadecyl aluminum, trieicosyl aluminum, tri(triphenyl methyl) aluminum, triduryl aluminum, tri(2,3-dimethyl- 1,3-butadienyl) aluminum, triterphenylyl aluminum, tripropyl aluminum, dimethyl cadmium, diethyl cadmium, dipropyl cadmium, dibutyl cadmium, diethenyl cadmium, dipropenyl cadmium, diisoamyl cadmium, methyl ethyl cadmium, dioctadecyl cadmium, dieicosyl cadmium, diphenyl cadmium, phenyl benzyl cadmium, phenyl ethyl ice cadmium, dialpha naphthyl cadmium, dicyclohexyl cadmium, dicycloheptenyl cadmium, di(phenyl cyclobutylene) cadmium, butyl cycloheptyl cadmium, di(2-methyl- 1,3-butadienyl) cadmium, di(butyl phenylene cyclohexylene) cadmium, didecenyl cadmium, dianthryl cadmium, diduryl cadmium, cyclohexyl phenyl cadmium, dimesityl cadmium, diisobutyl cadmium, dimethyl zinc, diethyl zinc, di-n-propyl zinc, di butenyl zinc, di-n-butyl zinc, diisobutyl zinc, diphenyl zinc, di-o-tolyl zinc, diethenyl zinc, dinonadecyl zinc, dicycloheptyl zinc, dicyclohexenyl zinc, dicyclobutyl zinc, di(1,1-binaphthyl) zinc, di(bicyclodecyl) zinc, di(1,3-butadienyl) zinc, ethyl benzyl zinc, didodecyl zinc, di(phenyl butylene) zinc, di(dodecenyl) zinc, di(cyclohexyl benzylene) zinc, di(methyl cyclohexylene) zinc, dieicosyl zinc, methyl tolyl cyclohexylene zinc, methyl cyclohexyl zinc, phenyl cyclohexyl zinc, dioctyl zinc, didecyl zinc, and the like, such as the Al, Cd and Zn alkyl, aryl, cycle-aliphatic, alkenyl, alkadienyl, cycloalkenyl, alkyl-aryl, aryl-cyclo-aliphatic, arylalkenyl, alkenyl-cycloalkenyl, alkyl-cycloaliphatic and alkyl-aryl-cycloaliphatic compounds and the like and mixtures of the same in which the alkyl, aryl groups etc. can be the same or difierent. Of these compounds it is preferred to use the dialkyl zinc compounds, especially those having from 1 to 10 carbon atoms.

If not readily available, the organometallic compounds can easily be prepared by methods well known to the art. For example, the trialkyl aluminum compounds are prepared from aluminum chloride and a Grignard reagent, and the triaryl aluminum compounds are prepared from aluminum and the mercurials. The organo cadmium compounds are best prepared from anhydrous cadmium chloride and a Grignard reagent. Synthesis of the alkyl zinc compounds is readily effected by the action of zinc on an alkyl iodide or on a mixture of an alkyl iodide and bromide, for example, C H I+Zn+ C H ZnI which when heated gives 2 C H ZnI (C H Zn+ZnI The diethyl zinc can easily be removed from the mixture. The diaryl zinc compounds are best prepared from the mercurials, for example,

The cycloaliphatic metallics can be prepared in similar ways as well as the mixed organometallics.

The inorganic oxide alone will not cause polymerization of the organic epoxide. Even when the oxide is dried or is heated at elevated temperatures, a process which will activate some materials for other polymerizations, it is not activated for the polymerization of epoxides. On the other hand the organometallics alone do not effect polymerization of the organic epoxides. However, when the oxide is treated with the organometallic, it becomes activated for the polymerization of organic epoxides. For example, the oxide can he treated with the organometallic in solvent, the resulting solution decanted from the solid and used again for three or more successive times for the treatment of additional new batches of the oxide. In each instance the organometallic activated the oxide for epoxide polymerization. Even when the activated oxide was washed several times with the solvent alone (free of organometallic), the oxide was still highly active for the polymerization of epoxides. Thus, the solvent washing should have removed all traces of the organometallic, yet the oxide was still activated. Hence, only small or minor amounts of the organometallic need be used to obtain the desired results.

It is not precisely known What occurs during treatment of the inorganic oxide with the oraganometallic compound. It may be that a complex or reaction product is formed or that small amounts of the organometalic remain absorbed on the oxide to in some fashion act on or with the oxide to serve as catalytic centers. On the other hand, it may be possible that the oxide holds the organometallic in such a fashion that it serves as an active site for the catalytic polymerization of the organic epoxide. In any event whatever may be the true explanation, it has been found that when the oxide is activated with the organometallic compound, materials are obtained which are very useful as catalysts for the polymerization of epoxide compounds.

A feature of the inorganic oxi=de catalysts of the present invention is that they require only relatively small amounts of the expensive organometallics in their manufacture to achieve the desired results in polymerization. Also, these activated oxide catalysts are less dangerous to handle than the organometallics when mixing them in the factory with the oxides and of which many may spontaneously ignite on exposure air. Hence, the novel catalysts of the present invention can be prepared by experienced personnel in high pressure laboratories and then delivered to pilot plants or polymer plants where they can be handled readily by less experienced personnel in charging the polymerization reactors. If a storage or handling vessel containing the novel catalyst breaks, or the catalyst is spilled, the danger to factory personnel of rapid spontaneous combustion is not present as when a large amount of the organometallic compound is being handled.

The inorganic oxide can be treated with the organometallic in mass or bulk as a liquid without solvent or in solvent. Where the organometallic is readily vaporized, or in the form of a vapor on gas, the vapor can be used to treat the oxide. Preferably, the organometallic is dissolved or dispersed in an organic solvent and the resulting material, preferably in solution form, is mixed and/or reacted with the oxide.

The amount of organometallic to use in treating the inorganic oxide can vary Widely. Very small amounts are effective while large amounts will prove wasteful. In general, there should be used only that amount which will be sufficient to activate the oxide. When the oxide is treated with a solution of the organometallic, somewhat larger amounts of the organometallic should be employed to obtain the desired concentration and to reduce the time involved. However, again, very dilute solutions can be employed. In general, especially when a solvent is employed during the initial treating step, the relative mol ratio of the organometallic compound to the inorganic oxide can vary from about 0.03:1 to 12.0: 1 while it is preferred that the mol ratio of the organometallic to the oxide be from about 0.1:1 to 3.5:1.

Instead of using batch processes to prepare the activated inorganic oxide, the oxide can be passed through a vessel in one direction while the metal organic in vapor form or in organic solvent is passed countercurrently through the moving bed of the oxide and then the organometallic withdrawn and recirculated to the vessel. The organometallic concentration can be maintained at a constant level :by bleeding in fresh supplies of the organometallic vapor, or solution of organometallic in organic solvent. The activated oxide is then withdrawn from the vessel.

It is preferred that heat be applied during the mixing or treatment of the inorganic oxide with the organometallic to expedite the time of treatment or activation of the oxide. However, reaction can be conducted in the cold or at temperatures below room temperature as well as at elevated temperatures up to below that of the decomposition or pyrolysis point of the oxide and/ or organo metallic compound. In general temperatures of from about 25 to 250 C. can be employed while it is preferred to employ temperatures in the range of from about 45 to 150 C.

The treatment of the inorganic oxide and organometallic should he conducted under non-oxidizing or inert conditions, for example, in the absence of air, oxygen, moisture and so forth. Although not too desirable, the reaction vessel can be flushed out with the vapor of the organometallic or solvent if used and the reaction carried out only in the presence of the vapor of the organometallic and/ or solvent. However, it is preferred to conduct the treatment in the presence of an inert gas such as nitrogen (preferably lamp grade), helium, neon, argon, krypton and other inert or non-reactive gas and the like and mixture thereof.

After the reaction or activation of the inorganic oxide with the organometallic, any excess or surplus amount of the organometallic can be removed if desired and the activated solid containing any residues used directly in the polymerization process. On the other hand the activated oxide can be used as the catalyst containing the excess organometallic alone or with the solvent, for example, while still somewhat wet with the same, in the form of a slurry, or as a dispersion in all of the solution of solvent and organometallic. The latter step is not too desirable as it results in some waste of the organometallic compound since any excess or surplus amount of the same can be used alone or with the solvent to activate other batches or quantities of the unactivated oxide. The excess organometallic as gas, in liquid form or in solvent can readily. be separated from the .oxide :by decantation, filtration,

centn'fugation, evacuation, and so forth.

The activated inorganic oxide may be stored at room temperature or below under an inert atmosphere. Prefer-1 ably, the catalyst is used in its freshly prepared form.

The activated inorganic oxide if agglomerated or in the form of chunks can readily be pulverized or powdered if desired prior to use in the polymerization process. The activated oxide can be added as such to the polymerization reactor or in an organic solvent as a slurry and so forth. The organometallic compound can be mixed with any solvent which is non-reactive or inert to the organometallic or inorganic oxide or which does not form a complex with the organometallic compound or oxide during activation of the oxide. The solvent should be a liquid at the reaction or treatment temperatures, especially from 25 to 250 C., and should be used in an amount sufiicient to dissolve the organometallic compound and provide a liquid medium. Generally, the solvent is used in an excess,

several mols, over the amount of the organometallic.- The organometallic-total solvent mol ratio, dependent to heptane,'2,6-dimethyl heptane, 4-ethyl heptane, 4-methyl heptane, octane, 2,7-dimethyl octane, isooctane, nonane, decane, undecane, tridecane, tetradecane, pentadecane, octadecane, eicosane, cyclohexane, methyl cyclohexane,

1,3-dimethyl cyclohexane, methyl cyclobutane, 1,4-dimethyl cyclohexane, isopropyl cyclohexane, cycloheptane, cyclopentane, benzene, amyl benzene, butyl benzene, s-v

butyl benzene, t-butyl benzene, 1,3-diethyl benzene, ethyl benzene, l-ethyl-4-isopropyl benzene, l-phenyl propane,

cumene, isodurene, pseudocumene, o-cymene, p-cymene, m-cymene, toluene, o-ethyl toluene, o-butyl toluene, p-- ethyl toluene, 3,5-diethyl toluene, propyl toluene, o-xylene,

4-ethyl-o-xylene, m-xylene, 4-ethyl-m-xylene, S-ethyl-mxylene, p-xylene, 2-ethyl-p-xylene, mesitylene and the like and mixtures thereof. In some instances liquid organic nonpolyrnerizable hydrocarbon unsaturated solvents can be employed such as those having at least 8 or 9 carbon atoms. Examples of such solvents are octylene, 1,1-diisopropyl ethylene, l-nonene, l-decene, Z-hendecene, 1-dodecene, tridecylene, l-tetradecene, cetene, menthene, betaphellandrene, ditriptene, conylene and the like and mixtures of the same with each other and with the aforementioned solvents.

The cyclic oxides to be polymerized include any cyclic oxide or epoxide having oxygen-carbon ring in which an oxygen atom is joined to 2 carbon atoms in the ring which will open and polymerize with the same or other epoxide monomers and having up to a total of 70 carbon atoms. These monomers, also, may contain 1, 2 or more, preferably only 1, aliphatic carbon-to-carbon double bond. The alkenyl, nitro, ether and ester substituted derivatives of these epoxides can likewise be employed. The use of monomer mixtures having epoxide monomers containing aliphatic carbon-to-carbon double bond unsaturation in an amount of from .about 0.5 or 5.0 to 15 or 30 mol percent or higher, the balance being the saturated epoxide monomer, permits the resulting copolymer to be cured readily with materials such as sulfur and the like. A very useful mixture is one containing propylene or butylene oxide in an amount of from about 97 to 99.5 mol percent and allyl glyeidyl ether, vinyl cyclohexene monoxide, or butadiene monoxide in an amount of from 3 to 0.5 mol percent to obtain a crosslinkable (by sulfur) copolymer. Minor amounts, from about 0.5 to 20 mol percent, preferably from 1 to mol percent, of a third, fourth or fifth etc. monomer, such as 1,2-butene oxide, 2,3- hexene oxide etc. of from 4 to 12 carbon atoms, can be present to break up or substantially entirely eliminate any crystallinity of the copolymer when desired, especially Where only small amounts of an unsaturated monomer are needed and more flexibility in processing and molding are desired.

Examples of useful cyclic oxides are ethylene oxide, propylene oxide, 1,2-butene oxide (or 1,2-epoxy butane), 2,3-butene oxide, 1,2-dodecene oxide (or 1,2-epoxy dodecane), isobutylene oxide, 1,2-pentene oxide, isopentene oxide, styrene oxide, 1,2-diisobutylene oxide, 1,2-hexene oxide, 2,3-hexene oxide, 1,2-heptene oxide, 2,3-diisobutylene oxide, allyl glyci dyl ether, isoheptene oxide, octene oxide, nonene oxide, decene oxide, 1,2-epoxy pentacosane, 1,2-epoxy heptacontane, hendecene oxide, methyl glyeidyl ether, ethyl glyeidyl ether, vinyl cyclohexene monoxide, nitro ethylene oxide, phenyl glyeidyl ether, 3-methyl3,4- epoxy butene-l, butadiene monoxide, glyeidyl methacrylate, dicyclopentadiene monoxide, isoprene monoxide, allyl epoxy stearate, and other epoxides. Preferably, these epoxides have a total of from 2 to 25 carbon atoms. Of these materials it is even more preferred to use the lower molecular weight monoepoxides such as ethylene oxide, propylene oxide, butylene oxide, etc., containing from 2 to 12 carbon atoms with minor amounts of unsaturated (ethylenic) mono-epoxides such as allyl glycidyl ether, butadiene monoxide and vinyl cyclohexene monoxide etc. containing from 3 to 12 carbon atoms. Mixtures of these epoxides can be used.

Those compounds which have no ethylene unsaturation may be cured with mixtures of organic peroxides and sulfur or other curing agents.

Moreover, blends or mixtures of polymeric materials can be prepared by this invention. For example, a polymer or copolymer prepared with the catalyst of this invention or by the use of other catalysts can be melted or dissolved in solvent and one or more epoxide monomers and the present catalyst added and polymerization continued to obtain another polymeric material made in situ with, or on, the original polymeric material.

The catalyst product or activated inorganic oxide is used in a minor molar amount only sufiicient to catalyze the reaction. Large amounts are usually wasteful and may in time cause reversion or subsequent decomposition of the polymer. In general, there is used a total of from about 0.01 to 20 mols of the catalyst product or activated oxide (computed as unactivated inorganic oxide solids) based on a total of 100 mols of the epoxide mon omer or monomers being polymerized. However, it is preferred to use a total of from about 0.5 to 16.0 mols of the activated oxide (computed as unactivated oxide solids) based on 100 mols of the monomer(s). The lower catalyst concentrations tend to give higher molecular weight polymers.

The monomers may be polymerized with the catalyst in bulk or in mass, preferred, or in solvent at lower temperatures for longer times. They, also, preferably should be polymerized under inert and/or non-oxidizing conditions, for example, under an atmosphere of nitrogen, argon, neon, helium, krypton or other inert or nonoxidizing atmosphere. It is sometimes desirable to polymerize in a solvent since this facilitates handling and operation. Alternatively, the inert gas can be omitted and the monomerpolymerized in the solvent only under pressure from any vaporized solvent or gaseous monomer. The monomer should be soluble in the solvent which should be an inert or non-reactive solvent. Examples of useful solvents are heptane, octane, cyclohexane, toluene, benzene, trimethylpentane, carbon tetrachloride, chloroform, diethyl ether, trichloroethylene etc. It is preferred to use non-polar hydrocarbon solvents such as those described above as well as those described With respect to the preparation of the catalyst. Since many of the monomers are volatile and to avoid oxidation, the polymerization should be conducted in a closed container under pressure. Polymerization can be conducted at temperatures of at least about 25 C., preferably at temperatures of from about 40 to C. or even higher.

In general, the catalyst, activated inorganic oxide, at room temperature or sometimes at the temperature at which it was prepared is placed in the reactor and the monomer or monomer and solvent added at room temperature and heat applied as necessary to effect polymerization. If the polymer dissolves in the solvent, it can be precipitated with a non-solvent and recovered, or the solvent can be separated from the polymer by evaporation etc. The catalyst product or catalyst residues can be removed if desired by centrifuging a solution of the polymer. If it is desired to destroy or kill the catalyst,

the polymer may be treated with water, alcohol solutions or dilute solutions of acids and the like. Alkaline materials may be used to neutralize the catalyst. The removal of the catalyst will depend upon the ultimate use of the polymer or copolymer. It is desirable to polymerize while agitating the reactants.

Since the reaction is exothermic and since some monomers may react very rapidly, it may be desirable to reduce the concentration of the catalyst product or to use a solvent or diluent as discussed above. Alternatively, the amounts of the catalyst product can be changed or the solvent eliminated to speed up the amount and rate of conversion or polymerization.

In the event that any gel forms and where it is not desired to have gel or a crosslinked (resinous) polymer but rather a rubbery or tacky solid polymer, inhibitors may be added. Examples of useful inhibitors are nitrobenzene, dinitrotoluene, dinitrodiphenyl, nitrodiphenyl amine, chlorodinitrobenzene .and so forth. In some instances gel formation may be avoided by polymerizing in the dark. These inhibitors, also, are desirable to use to prevent premature gelling or crosslinking when the polymers are compounded on a rubber mill or in a banbury, etc. Antioxidants such as phenyl beta naphthylamine, also, are desirably added prior to or during polymerization.

Many of the polymers and copolymers etc. obtained by the method of the present invention have a high average molecular weight, i.e., from about 20,000 to 500,000 or higher, as shown by their high viscosities. They may be crystalline and/or amorphous. The resinous and rub bery polymers and copolymers, alone or in admixture with each other, are useful as coatings for fabrics, films for packaging materials, elastic fibers or thread, golf balls, adhesives, and in making tires, shoe heels, rain coats, gaskets, printing rollers, and upholstery materials, floor mats and tiles, sponges, rubber shoes, molded articles, bumpers, motor mounts, encapsulating compounds and the like. Low molecular weight solid or grease-like polymers of this invention are useful as plasticizers for natural and synthetic resins and rubbers.

The polymers, including copolymers, of this invention may be compounded with the usual rubber and resinous 8 These results show the need for the activation of the antimony trioxide by the organometallic, since neither material is a catalyst by itself.

Example II compounding materials, such as curing agents, antide- 5 gradants (stabilizing agents, antioxidants, antiozonants, 111 a PYfeX g s be 2 gm. of 1203 (drled at etc.), fillers, extenders, reinforcing agents, ultraviolet for were act1Vat ed y hejatmg 1 hour at light absorbers, fire resistant materials, dyes, pigments, Wlth 2 ZHEtz dlssolved 111 20 'Y P plasticizers, lubricants, other rubbers and resins and the under a nltfogen atmosphere- Aft'irwal'ds thfi llquld like. Examples of useful materials which can be com- 10 z-l 'z rs) was decanted and f rr d to asecond pounded with these rubbers, resins and polymers are zinc tube Whlch l had 2 z ame lva lon oxide, stearic acid, sulfur, Z-mercaptobenzothiazole, bis- P here and the hquld Was transferred to. (morpholyl) disulfide, bis(benzothiazyl) disulfide, bisa t g tube and afterwards t a fourth one, each 9 (morpholyl) tetrasulfide, zinc dimethyl dithiocarbamate, tammg 2 Sb203 e the a 31 tetramethyl thiuram disulfide, carbon black, TiO iron 15 f P After t 6 last acnvatlon tube) e llqllld was decanted from the Sb O and it was observed oxide calcium oxide S10 and S10 contamlng materials,

to have finely divided particles of antlmony tnoxrde susalum1nurn oxide, phthalo .cyanrne blue or green, asbestos, pended in it sihcon monoxlde mlca Wood g g or ceilulosi The 4 samples of activated Sb O and the finalliquid fibers or flock a bfu'ytesa dlocty p mcresyl 20 sample were used as a catalyst material to polymerize Phosphate, 11I1I n1grat mg P PIaFtICIZeIS PPeny 13.4 ml. (0.2.mol) of dry propylene oxide under nitrogen. t naphthylamme, P numeral The polymerization took place for 24 hours at 80 C. monobenzyl ether, mixtures of octylated drphenylammes, and the Polymers were Worked up by dissolving them in styfenated P aldol alpha naphthylamllfe, dlphenyl acetone with phenyl beta naphthylamine, centrifuging. amine acetone reaction Products, antimony Oxide, asphalt, 25 the solution, and pouring the clear acetone solution into coumarone indene resin, natural rubber, polyisoprene, water. The polymers obtained were rubbery. butadienestyrene rubber or resin, nitrile rubber, acryl- The results obtained with the four activated Sb O onitrile-styrene resin, polyester and/or ether urethanes, samples and the liquid suspension are shown below:

Percent Inherent Run No. Catalyst Couver- Vise. in Percent Remarks sion benzene Ash at 25 C.

II-A 2 g. SbgOa activated by 2 ml. ZllEtg 77 3. 57 0. 92 1.2 g. Sb Oa rein 20 m1. heptane, 1 hr. at 80 C. ouperated from under N2. Liquid transferred to the polymer. next tube. 11-}; 2g. SbzOz activated iorl hr. under N 86 3.86 0.69 1.4 g. SbzO; re-

at 80 C. by liquid coming from cuperated from previous tube (Run A), decanted. the polymer. lI-C 2g. SbzOz activated for 1 hr. under N2 95 3.61 1. 15 2.2 g. SbzO; re-

at 8 O. by liquid coming from cuperated from previous tube (Bun B), decanted. the polymer. II-D 2g. Sb203 activated forl hr. under N2 77 2.25 1.03 1.5 g. SbgOa reat 80 C. by liquid coming from cuperatcd from previous tube (Run 0), decanted. the polymer. II- Ligand left from previous tube (Run 77 3. 85 0.87

polyvinyl chloride, vinyl chloride-vinylidene chloride copoloymers, and the like and mixtures thereof.

The following examples will serve to illustrate the present invention with more particularity to those skilled in the art:

Example I In a bottle there are heated 2 gm. of Sb O previously dried in an oven at 150 C., in suspension with a 2 ml. of diethyl Zinc (ZnEt dissolved in ml. of dry heptane for 1 hour at 80 C. under nitrogen. The special design of the bottle allows the contents to be filtered, leaving the solid inside without contacting the air. After the heptane solution of the ZnEt was filtered off, there were added to the activated Sb O 13.4 ml. of propylene oxide (0.2 mol) and the mixture was heated at 80 C. for 24 hours under nitrogen to polymerize the propylene oxide.

After extracting the polymer with acetone, centrifuging the acetone solution, pouring it into water and drying the polymer, the conversion of monomer to polymer was 86%. The inherent viscosity of the polymer in benzene was 5.98 (0.2148 gm. polymer in 100 ml. benzene at 25 C.).

When the same polymerization procedures was followed using diethyl zinc alone, no polymer was obtained after 48 hours at 80 C. Also, when the antimony trioxide, dried in an oven at 150 C. or dried for 16 hours at 500 C. in nitrogen, was used alone, no polymer was obtained after a polymerization time of 48 hours at 80 C.

These results show that the inorganic oxide need only be treated with very small amounts of the organometallic compound to achieve the desired results or that the same liquid can be used to activate several batches of the inorganic oxide.

In a separate experiment 12 g. of Sb O (dried at 150 C. for 48 hours) were treated for 1 hour at C. under nitrogen .with 10 ml. of diethyl zinc dissolved in ml. of heptane. The activated Sb O was then washed three times with 100 ml. of heptane in each case and decanted after each washing, filtered on a glass filter and washed once again with heptane. The zinc content of the activated Sb O was 2.45% (spectroscopy analysis). This value corresponds to about 0.11 mol of diethyl zinc for each mol of Sb O Example 111 In a Pyrex glass tube there were added 2 gm. of Sb O (direct from the bottle, not previously dried), 20 ml. of,

dry heptane (dried by passing it through molecular sieves), and 2 ml. of ZnEt under nitrogen.

The tube was heated for 1 hour at 80 C. in a watery bath. After cooling down the tube to room temperature,

ofl? the solvent at reduced pressure. After drying, the conversion to polymer was 57%. The inherent viscosity of the polymer was 0.809 (in benzene), and its ash content was 0.24%.

10 Example VI 2 g. Sn were heated at 80 C. for 1 hour under N with 2 ml. diethyl zinc in 20 ml. heptane. The liquid was decanted from the SnO and added toa fresh batch anothar run 2 of 20 of 2 5 of 2 g. of smo which were heated with the liquid for 1 of ZnEtZ of prcipylepe oxide were mlxed hr. at 80 C. under N The liquid was decanted from togoether under mtmgen.and thls nilxtum f at the second batch of SnO To the activated SnO (secfor 24 Wlthout Prevlous activation of the 0nd batch) was added 13.4 ml. of propylene oxide and the oxlde The cfmverslon to polymer was only 10% land the resulting mixture was heated at 80 C. for 24 hours. The obtamed was a grease rather than '5 10 resulting polymer was worked up in a manner similar to T1118 shows the neclgsslty fol-Pumacnvatlon to that of the preceding example. 1.7% conversion to of 3 e morgamc oxlde to obtam high ylelds of rubbery a rubbery polymer was thus obtained This example pr ucts.

Example 1V shows that staurnc oxide is a polymerization catalyst for epoxrdes.

2 gm. of antimony pentaoxide were mixed with 2 ml. Example VII of ZnEt in ml. heptane under nitrogen. The resulting mixture was heated for 1 hour at 80 C. The re- Stannous oxlde Q act'lvated and used as sulting mixture was decanted leaving the activated Sb O caialyst for the polYmfrnzatlon (111 mass) of proPylene which was mixed with 13.4 ml. of propylene oxide under 20 Pxlde 111 a manner slmllar to the methods of the P nitrogcn and heated to 80 C. for 24 hours. The polymer g CXHIHPIeS- The Procedures employed and Tpersults obtained was worked up with acetone and phenylbetatained are shown below:

PZN PZN Conver- Appearance of Work up Procedure Run N o. Monomer Catalyst Time, hrs. Temp., C. sion, t Product percen VIIA 13.4 ml. P.O- 2g.SnO activated by 2ml.ZnEt in20 ml. 24 80 0.8 Rubbery Acetone, PBNA,

heptane. 1 hr. at 80 C. under N3. pouring into H2O. Liquid decanted from solid SnO. VIIB l do 2 g. SnO activated with liquid (ZnEt,-i+ 24 80 3.4 do Acetone, PBNA,

01H solution from previous Run VII- pouring into H10. A) for 1 hr. at 80 C. under N, decanted llqurd from solid Sn 0. VILC--- do 2 g. SnO activated wlth liquid from pre- 24 80 6.8 do Acetone, PBNA,

vious tube (Run VII-B) for 1 hr. at 80 pouring into H20. {23. gnder N g, decanted liquid irom solid 11 VIID .do 2 g. SnO activated with liquid from pre- 24 80 *9 do Acetone, PBNA,

vious tube (Run VII-C) for 1 hr. at 80 pouring into 1120. g. (1)1nder N;, then decanted from solid Inherent viscosity in benzene at C. was 5.29; percent ash was 1.09.

Example V In a Pyrex polymerization glass tube there were heated This example shows that stannous oxide is a polymerization catalyst for epoxides. PBNA is phenyl beta naphthylamine.

Example VIII The method of this example was similar to the methods of the first two paragraphs of Example I, above, except that the 813 0 was washed with heptane after the liquid had been decanted from the activated solid and before adding the propylene oxide. The procedures employed and results obtained are shown below:

2 gm. CrO with 1.3 ml. ZnEt dissolved in 20 ml. dry

Conver- Appearance of Run No. Catalyst sion, Polymer Polymer Workup Inh. Visc.*

percent Product VIIIA 2 g.Sb=O activated by mixing with 2 1111. 89.6 Rubbery- Acetone-PBNA, pouring 3.50

ZnRt; in 20 ml. heptane (1 hr. at 80 C.) mto H 0. under N Liquid decanted. Oxide washed once with 20 ml. pure heptane. VIIIB 2 .sb,o3 activated as above Run VIII-A 92.2 (10 .-d0 7.64

(fresh ZnEt, and heptane) but washed twice with 2 separate batches of 20 ml. each of essentially pure heptane. VIII-0--.. 2 g.Sb,O activated as above Run VIII-A, 93 d0 ..do

(fresh ZnEt; and heptane) but 3 washings with 3 separate batches of 20 ml. each of pure heptane.

*In benzene at 25 C.

These results show that reasonable washing of the catalyst to remove theoretically any residual ZnEt does not destroy its eifectiveness but may even increase yields and viscosities.

Example IX In a polymerization tube 2 g. of boron oxide, B 0 were mixed with 2 ml. ZnEt in 20 ml. of heptane and the resulting mixture was heated for 1 hour at 80 C. under an atomsphere of nitrogen gas. After cooling to room temperature, 13.4 ml. of propylene oxide was added with- 1 1 out decanting the solution and polymerization conducted for 24 hours at 80 C. The contents of the tube were then poured into benzene, a dilute solution of HCl added, water was then added, and the benzene and HCl-water 12 These results show that the activated catalysts of the present invention are useful for the polymerization of certain saturated and unsaturated epoxides but are not useful for the polymerization of oxetanes, furans, thiofurans layer Separated The benzene layer was evaporated to or chlorinated oxetanes or .epoxides at reasonable temr yield a greasy polymer representing a yield of 18% and peratures and tunes E l X" having an inherent viscosity in benzene at 25 C. of xamp 8 0.441. The method of this example was similar to the method E l X of the first paragraph of Example I, above, except that 1 th d the monomer used was a monomeric mixture of propyl- The method of thls exam? e was sum at to e metho ene oxide and allyl glycidyl ether in the mol ratio of about of the first two PaTagra'Phs of Example above and 97 :3. Several runs were made. Samples of the cot method mcludmg the Washmg step of Examplejvmi polymer were then compounded and used. In one series above, eXCePt that the Organometalhc used Was tl'lethyl the activated Sb303 was removed (acetone-centrifugationaluminum instead of diethyl zinc, and one of the inorganic water) f th Copolymer hile i the second series it oxides used was SnO The procedures followed and the was not removed from the copolymer prior to comresults obtained are shown below: pounding and curing. Copolymers were also cured with Polymerization Recipe PZN PZN Run No. Time Temp. Conver- Appearance of (111s) C.) sion, Product Momoner Solvent Catalyst Percent XA 26.8 ml. PO, Bulk 2g. SnOgactivated by 2ml.AlEt;in20ml. 24 80 14 Grease.

heptane. 1 hr. heating at 80 C. under N1. Liquid decanted. Solid S110] washed once with ml. pure heptane before use in polymerization. X-B 26.8 ml. PO ..d0 2 g. SD10; activated by 2 ml. AlEt; in 20 24 80 17 Rubber.

' ml. heptane. 1 hr. heating under N 7 at 80 0. Liquid decanted. Solid Sb O; then washed once with 20 m1. pure lreptane before use in polymerization.

These results show that other organometallics can be used for the activation of the oxides.

Example XI The method of this example was similar to the method of the first two paragraphs of Example I, above, and to Material:

and without carbon black. The compounding recipe was as follows:

Partsby weight Copolymer (97:3/POzAge) 100 Phenyl beta naphthylamine 1 Philblack E (carbon black) as indicated below 40 tr-rloulN the general method disclosed in Example II, above, ex- Steam-c acid cept that other monomers were employed during the Zinc oxide polymerization runs. S lfu The procedures followed and the results obtained are Tetramethyl thiuram disulfide shown below: BIS (bcnzothlazyl) drsulfide Run No Monomer (no solvent used) Catalyst PZN Time PZN Percent Appearance 01 Hrs. Temp. 0. Conversion Polymer Product XI-l 13.5 ml. epichlorhydrin 2 g. SbrOa activated by 2 ml. ZllEtr in 20 ml. hep- 24 N o PZN tane, 1 hr. heating at 80 under nitrogen. Liquid taken away from solid activated SbzOs before polymerization. XI-2 20 ml. diethyl oxetane 2 g. SD20; aetivatedf as above run l-new prepara- 24 80 No PZN tion, liquid removed. XI-3 20 ml. AGE 2 g. SbgOs ectivatedl' as above run l-new prepara- 24 80 Rubber-y.

ation, liquid removed. XI-4 20 ml. styrene oxide 2 g. SbzOs activatedf by the liquid preceding trom 24 80 100 Do.

run 1, liquid removed trorn this SbrOa. XI-5 20 m1. phenylglycidyl 2 g. SbrOa activatedt-by the liquid proceding from 24 80 100 Hard solid.

her. run 2, liquid removed from the SbgOa. XI-6 20 ml. THF 2 g. S1320; activatedt by liquid proceding from run 24 80 No PZN 3, liquid removed from this SbzOz. XI-7 20 ml. 3,3-diehloromethyl 2 g. Sb203 activatedt by the liquid coming tromrun 24 80 N o PZN oxetane. 4, liquid decanted trom SbzOa. XI-S 20 ml. tetra hydrothio- 2 g. SbzOa activatedi' by the liquid coming from 24 80 No PZN phene. run 5, liquid taken away from SbgOa. XI-9 20 ml. thiopheue 2 g. SbiOa aetivatedt by the liquid coming from 24 80 No PZN run 6, liquid taken away from Sb Oa. XI-lt) 13.4 ml. PO 2 g. SbzOa aetivatedt by liquids coming from 3 80 37 Rubbery.

previous activations, runs 7, 8, 9, liquid taken away from Sb Oa before polymerization. X-ll 20 ml. l,4-dichloro-2,3- 1.5 g. Sb O; activated by 2 ml. ZnEt, in 20 ml. 24 80 N0 PZN epoxy butane. heptane for 1 hr. at 80 C. under N1. Liquid taken away.

Norns: AGE-allyl glyeidyl ether, THF-tetrahydrofuran, PO-propylene oxide, and PZN-polymerization.

This run conducted to check, it the liquids trom runs 7, 8, and 9 were still active to activate the SD20: for the polymerization of propylene oxide.

11 hour at 80 C. under N1.

Cured Properties 01' Copolymers Activated SD10; Left in Copoly'mer Activated Sb Og Removed from Copolymer Cure 30 Min. at Cure 50 Mei. at Cure 30 Min. at Cure 45 Min. at 285 F. 285 F. 285 F. 285 F.

' 11-1 131-1; 'A-2 B2 A-3 13-3 A4 IB-4 Tensile Strength, p.s.i 1, 509 2, 475 750 2, 550 2, 425 2, 475 2, 675 2, 725 Percent Elongation 650 600 440 480 760 620 750 580 300% Modulus, p.s.i 281 1, 125 325 1, 500 225 1, 050 225 1, 275 Shore A Durometer 49 76 47 75 50 71 46 72 *A, No carbon black. T B", With carbon black.

From the above data, it is apparent that the black stocks with the activated Sb O removed and with the activated Sb O remaining in the copolymer show someing the amount of ash (catalyst residue) from the polymer obtained. The amounts of antimony trioxide and zinc diethyl used, the inherent viscosity of the polymer and the what similar physical properties. The tensile properties 20 amount (conversion) of monomer to polymer are shown of the non-black stocks are better when the activated below:

Grms. Millimol of Millimol ZllEtq/ Inh. Vise. in Conver- Run No. Sb O ZllEtg Grms. 810 isopropanol sion, perat 60 0. cent 1 1 1 Traces 1 2 2 Traces 1 5 5 2. 43 14 1 7 7 3. 53 25 1 10 10 1. 50 40 1 15 1. 92 81 1 25 3. 62 85 1 30 2. 70 67 2 1 0. 5 1. 7 2 2 1 5 2 6 2. 5 3. 16 95 2 7 3. 5 2. 38 98 2 10 5 1. 98 99 2 15 7. 5 95 2 25 12. 5 77 5 1 0. 2 4. 91 8 5 2 O. 4 5. 81 94 5 5 1 1. 76 99 5 7 1. 4 1. 68 100 5 10 2 1. 39 98 5 15 3 2. 32 76 5 25 5 1. 30 98 Sb O has been removed, although it will be appreciated that tensile properties of non-black stocks are extremely sensitive to the state of cure.

Samples of compounded and cured copolymers, A-2 and B-2, above, were aged at 300 F. for 24 hours and then tested and compared with the unaged copolymers. The results obtained on testing are shown below:

after aging shows that it is not always necessary to re move the activated oxide from the polymer.

Example XIII Antimony trioxide (Sb- 0 was suspended in 20 ml, of heptane (dried over molecular sieves) in a tube reactor under nitrogen and diethyl zinc added. The tube was then heated for 1 hour at 80 C. and cooled to room temperature. After cooling there was added to the tube 0.25 mol of propylene oxide and polymerization conducted at 80 C. for 4 hours. After polymerization the contents were diluted with benzene containing some phenyl beta naphthylamine. The benzene solution of the polymer was filtered or centrifuged to separate the residual Sb O and the solvent removed from the polymer by stripping under a vacuum. The conversion was computed after subtract- It is to be understood that in accordance with the provisions of the patent statutes, the particular compositions, products and methods described and set forth herein are presented for purposes of explanation and illustration and that various modifications of said compositions, products and methods can be made without departing from this invention.

What is claimed is:

1. The method of making a substantially linear polyether which comprises, under an inert atmosphere, mixing together at least one mono 1,2-epoxide and a catalyst composition and polymerizing said epoxide through its epoxide group in the presence of said catalyst composition at a temperature of at least about 25 C., (A) said epoxide having from 2 to 25 carbon atoms and being free of halogen atoms, and (B) said catalyst composition comprising an oxide selected from the group consisting of antimony trioxide, antimony tetraoxide, antimony pentaoxide, boron oxide, chromium trioxide, stannous oxide and stannic oxide and mixtures of said oxides, said oxide being activated for the catalytic polymerization of said epoxide by contacting said oxide with at least one organometallic compound selected from the group consisting of AlR CdR and ZnR where R is a hydrocarbon radical of from 1 to 20 carbon atoms and is free of aliphatic unsaturation, and said catalyst composition being used in a minor molar amount as compared to said epoxide and sufiicient to polymerize said epoxide to the solid state, said organometallic compound being used in an amount sufficient to activate said oxide for the polymerization of said epoxide.

2, The method according to claim 1 in which the polymerization of said epoxide is conducted in an inert organic solvent for said epoxide and where said organometallic has been used to contact said oxide in the mol 15 ratio of organometallic to oxide of from about 0.03:1 to 12.0: 1.

3. The method according to claim 1 in which the relative proportions of said catalyst composition computed as unactivated oxide solids to said epoxide are fromlabout 0.01 100 to 20: 100 moles, in which the temperature during polymerization is from about 40 to 150 C., and in which said ox-ide has been contacted with said organometallic compound at a temperature of from about 25 to 250 C.

4. The method of making a solid substantially linear polyether which comprises, under an inert atmosphere, mixing together at least one mono-1,2-epoxide and a catalyst composition and polymerizing said epox-ide through its epoxide group in the presence of said catalyst composition at a temperature of from about 40 to 150 C., (A) said epoxide having from 2 to 12 carbon atoms and being free of halogen atoms, and (B) said catalyst composition comprising an oxide selected from the group consisting of antimony trioxide, antimony tetraoxide, antimony pentaoxide, boron oxide, chromium trioxide, stannous oxide and stannic oxide and mixtures of said oxides, said oxide being activated for the catalytic polymerization of said epoxide by contacting said oxide with at least one organometallic compound in an inert liquid organic solvent for said compound and at a temperature of from about 45 to 150 C. and being selected from the group consisting of AlR CdR and ZnR where R is a hydrocarbon radical of from 1 to 20 carbon atoms and is free of aliphatic unsaturation, said organometallic compound being used to contact said oxide in the mol ratio of organometallic to oxide of from about 0.111 to 3.5 :1, and the [relative proportions of said catalyst composition computed as unactivated oxide solids to said cpoxide being from about 0.5:100 to 16:100 mols.

5. The method according to claim 4 in which said organometallic compound is diethyl zinc.

6. The method according to claim 5 in which said oxide is antimony trioxide.

16 7. The method according to claim 5 in which said oxide is antimony pentaoxide. i

8. The method according to claim 5 in which said oxide is boron oxide.

9. The method according to claim 5 in which said oxide is stannous oxide.

10. The method according to claim 5 in which said oxide is stannric oxide.

References Cited by the Examiner UNITED STATES PATENTS 2,870,100 1/1959 Stewart et a1, 260 2,905,646 9/1959 Natta et al. 252-431 2,908,674 10/1959 Nowlin et al. 252-431 2,946,778 7/1960 Ke et al. 252-431 2,952,643 9/1960 Voge 252-430 2,971,942 2/1961 Masters et. al. 2602 2,992,193 7/1961 Porret et a1. 2602 3,014,893 12/ 1961 Susman et a1 260-47 3,037,008 5/ 1962 Garetzon et al. 252-430 3,073,799 1/1963 Skifi 26047 OTHER REFERENCES WILLIAM H. SHORT, Primary Examiner.

LOUISE P. QUAST, HAROLD BURSTEIN, JOSEPH R, LIBERMAN, Examiners.

J. E. ALIX, S. P. SULLIVAN, S. N. RICE, T. PERTIL- LA, Assistant Examiners. 

1. THE METHOD OF MAKING A SUBSTANTIALLY LINEAR POLYETHER WHICH COMPRISES, UNDER AN INERT ATMOSPHERE, MIXING TOGETHER AT LEAST ONE MONO 1,2-EPOXIDE AND A CATALYST COMPOSITION AND POLYMERIZING SAID EPOXIDE THROUGH ITS EPOXIDE GROUP IN THE PRESENCE OF SAID CATALYST COMPOSITION AT A TEMPERATURE OF AT LEAST ABOUT 25*C., (A) SAID EPOXIDE HAVING FROM 2 TO 25 CARBON ATOMS AND BEING FREE OF HALOGEN ATOMS, AND (B) SAID CATALYST COMPOSITION COMPRISING AN OXIDE SELECTED FROM THE GROUP CONSISTING OF ANTIMONY TRIOXIDE, ANTIMONY TETRAOXIDE, ANTIMONY PENTAOXIDE, BORON OXIDE, CHROMIUM TRIOXIDE, STANNOUS OXIDE AND STANNIC OXIDE AND MIXTURES OF SAID OXIDES, SAID OXIDE BEING ACTIVATED FOR THE CATALYTIC POLYMERIZATION OF SAID EPOXIDE BY CONTACTING SAID OXIDE WITH AT LEAST ONE ORGANOMETALLIC COMPOUND SELECTED FROM THE GROUP CONSISTING OF ALR3, CDR2, AND ZNR2, WHERE R IS A HYDROCARBON RADICAL OF FROM 1 TO 20 CARBON ATOMS AND IS FREE OF ALIPHATIC UNSATURATION, AND SAID CATALYST COMPOSITION BEING USED IN A MINOR MOLAR AMOUNT AS COMPARED TO SAID EPOXIDE AND SUFFICIENT TO POLYMERIZE SAID EPOXIDE TO THE SOLID STATE, SAID ORGANOMETALLIC COMPOUND BEING USED IN AN AMOUNT SUFFICIENT TO ACTIVATE SAID OXIDE FOR THE POLYMERIZATION OF SAID EPOXIDE. 